A Brief History of Batteries- Part 2

Last week I posted on the need to understand the history of battery development and how this will influence the future of batteries.  We conclude today with Part 2 of this series. 

Chapter 3:  If it is sparingly soluble, then lets talk. 

The lead acid battery is the first rechargeable battery ever made.  Its endurance over 150 years is a testimony to its robustness (or to the fact that battery researchers can’t seem to find anything better even after 150 years.  It is all a point of view!). 

The lead acid battery undergoes what is called dissolution-precipitation.  This is the mechanism by which charge/discharge occurs in the battery.  Basically, you dissolve the compound in solution and then it precipitates out.

The behavior of the lead-acid battery is remarkably similar to that of the zinc electrode in a Zn-manganese oxide alkaline battery or for that matter to the lithium thionyl chloride battery.

But if the lithium thionyl chloride is not a rechargeable battery and the zinc-manganese oxide is not a rechargeable battery, then why is the lead acid a rechargeable battery? 

This is because the lead sulfate is soluble in sulfuric acid (which is the electrolyte) unlike the lithium chloride.  But it’s not as soluble as the zinc oxide in potassium hydroxide.  

Its solubility is not too much, nor too little.  It’s just right!  It’s referred to as a sparingly soluble salt. 

This feature of having sparing solubility is critical in making a battery that undergoes dissolution-precipitation recharge. 

This occurs because the reactants and the products are right next to each other.  This means that when you go in reverse, there is a high probability that things go back to the same place where they came from.  Not having something move around is a great way to prevent shape change.

Once you understand that solubility is key you begin to understand the decades that were spent on trying to change the solubility of zinc oxide in electrolyte using various techniques.  And you begin to start thinking about ways to encapsulate the zinc.  And you begin to wonder if you should never let the zinc precipitate as zinc oxide and if you should just keep it as zincate by, say, flowing it. 

All these perfectly valid ideas start to make a lot of sense.  What you can’t answer is if these ideas will succeed in solving the fundamental problem with the zinc electrode. 

But we should remember that in general, the lead-acid is not the greatest battery in the world when it comes to recharging.  Think sulfation.   Remember the blog post on battery rules where I Haiku-ed my way to better battery life?  Remember that sulfation occurs in the discharged state. 

The reason for this is also fundamentally connected to this dissolution-precipitation mechanism.  On the one hand, this mechanism allows you to make a good rechargeable battery, on the other hand, it also causes it to die in time. 

Moral of this story:   If you want good rechargebility, dissolution-precipitation is not a good idea, although we may be able to live with it.    

Chapter 4:  And you thought electroplating was easy.

Electroplating has been a gift that has been giving for decades.  Probably the last big development was the via-hole plating of copper for making semiconductor chip interconnects. 

In general, plating something uniformly is not easy, but it’s not an unsolvable problem either.  We do have a lot of smoothly plated stuff all over the place. 

This is until you try plating lithium (and a few other metals, including zinc).   Plating lithium is sort of important because this would be the charging reaction if you want to make your watch battery a rechargeable battery or if you want to make a Li-sulfur or Li-air battery rechargeable. 

People spent much of the 2-3 decades of the last century trying to make a rechargeable lithium (watch) battery.  The last time I check, I was asked to buy a new watch battery and not try to recharge it. 

This is because, in the case of lithium, the plating results in dendrites and lead to shorting of the battery. 

The reason for this starts with surface inhomogeneities that lead to nucleation of the deposition process in one spot, after which ohmic and transport effects lead to further amplification of this inhomogeneity.

That complicated paragraph is tying to tell you that it plates out like a needle sticking out of the electrode.  The needle can puncture through the separator and short to the cathode.  As I keep mentioning in these blog posts, shorting a battery is not a good idea.  Really, it is not.

Same problem happens in the zinc electrode.  Zinc wants to plate out as a dendrite instead of a smooth surface.  Same reasons as above. 

Every electrochemist that learns of this issue immediately thinks of 10 things to try that could solve the problem.   Turns out all 10 ideas probably don’t work.

There have been, literarily, thousands of studies on trying to solve this issue.  The most promising appears to be using a separator that is hard and prevents the dendrite from growing. 

But as of today, we do not have a method to prevent lithium dendrites at room temperature and give us good power capability.  It’s a problem that is still around. 

The moral of this story:  If your battery requires you to plate out a metal, it is probably going to be an issue achieving good rechargebility. 

And if you want to make a rechargeable Li-air or Li-S electrode, getting the lithium to recharge is, I’m pretty confident, a pre-requisite. 

Epilogue:  Rules to live by. 

So how do we make a rechargeable Li-S and Li-air (or zinc-air) battery?

If I knew that I would not be writing blog posts!

But we need to beat three things that history has taught us: 

1.     Avoid electrodes that require a plating reaction. 

2.     If you have a product that is highly soluble, you are in trouble

3.     If you don’t have any solubility, its worse

One can avoid all this by finding systems where no structural changes happen.  Thus were born systems like Ni-MH, Li-ion, and Ni-hydrogen.  These systems have their own problems, but atleast we are starting with something that has certain inherent advantage.   I will elaborate on these problems in the very near future when I delve into the present-day developments in batteries. 

But suffice to say, if you want to make the battery of the future, then you have to beat the three issues listed above. 

Along the way, you may make the batteries of the past also work.  

Venkat

In batteries, 2+2=1. Actually more like 1/2. Well... maybe a bit less.

This is a blog post I've wanted to write for a decade. The reason I haven't (other than the obvious problem that a decade ago, I did not know what a blog was!), is because its a tough post to write. But, folks tell me that I have a gift for explaining things (I use the world "folks" is a generic sense to indicate a number greater than 0), so I shall try.

Everyone wants to make a better battery. What they mean when they say "better" is a battery that has more energy. This is what many (not all) battery researchers are trying to do, and this is what every user wants. If you read my post titled "A Moore's law for batteries? Maybe not", you will know that the game is to find new materials that make up the anode and cathode of a battery.

The idea here is to find a new material that has more capacity than the existing material and/or find one that operates at a higher voltage. Capacity is a measure of the amount of charge (electrons) you can get per gram. More is obviously better. Capacity times the voltage is energy; for real-world applications what matters is the energy. Typical numbers for capacity for lithium-ion batteries would be 140 mAh/g for the cathode and 330 mAh/g for the anode. The typical voltage of a lithium-ion battery is 3.7 V.

A lot of research in lithium-ion batteries is focussed on increasing the capacity. There is also an active area of interest in increasing the voltage to above 3.7 V. Increasing the voltage is going to be hard (very hard), so increasing the capacity appears to be the way batteries will improve, atleast in the short-term.

Simple enough.

Those of you who are paying attention have probably noticed that for every gram of material, you only have ~1/2 the capacity in the cathode compared to the anode. If you want to make a battery with a capacity of, say 330 mAh, then you have to take 1 gram of the anode, but you need 2.35 g of the cathode (330/140). What this means is that you have a total weight of 3.35 g to get a capacity of 330 mAh. So the capacity of your battery is actually 98 mAh/g (330/3.35). So you started with a anode at 330 mAh/g, a cathode at 140 mAh/g and you get 98 mAh/g for the battery. A 2 mAh/g cathode with a 2 mAh/g anode give you a 1 mAh/g battery. 2+2 is actually only 1. Certainly not 4. Not even 2! Welcome to batteries.

If you have a new anode with say 10 times the capacity (so 3300 mAh/g) you can do the same math and you will get a cell capacity of 134 mAh/g (for a battery of capacity 3300 mAh the weight is 24.5 g). You go to all this effort to make something 10 times better and you get to use your iPhone for an extra 30% talk time. A bit disappointing! On the other hand, if you had an cathode that was, say, twice as good, at 280 mAh/g (with an anode at 330 mAh/g), then your cell capacity goes up to 151 mAh/g. Much better. 50% better. This is why most researchers want to find a better cathode. Its more bang for the buck.

All this is pretty simple. All battery folks know this. 2+2=1. End of story.

Or is it? There is another small factor that even battery researchers sometimes miss. This factor is the dead weight in a battery.

If you really want to use the anode and cathode, you need some extra real estate. Things like separators to keep the electrodes apart, current collectors to collect the current, and packaging to make sure you contain it in a neat little package. All these add weight and volume. It doesn't matter if you have 10 times the capacity in a new anode, you still have to carry this dead weight.

This is a lot like a gasoline-powered car. Only the gasoline has any useful energy in the car. But to use the gasoline, you need a tank, an engine, the wheels, the drivetrain.... you get the point.

Obviously, if you can make the weight of the rest of car as light as you can (no seats?), it helps you get more from your tank of gas. Similarly, if you can minimize the amount of unwanted weight, it helps a lot in the battery. What this means is that you try to increase the ratio of the active materials (the anode and cathode) to that of the inactive material (the separators, current collectors etc).

But there is a catch. Turns out that you can't increase the amount of the active material willy-nilly. It has to do with losses in a battery. If you put extra active material in, you have to add a bit of the inactive with it. And increasing the amount of active materials involves making the anode and cathode thicker and there is a limit to how thick these can be made before losses become prohibitive. One needs to account for these factors.

*Geek meter on*

Remember the example above where we calculated 98 mAh/g using a battery of capacity 330 mAh with a weight of 3.35 g? If you do the math on the extra weight for the inactive material, you have to add an extra ~3.35 g. You can do the math to convince yourself of this number or you can trust me. I would suggest doing the latter. So you actually only get a capacity of 49 mAh/g (1/2 of 98)! 2+2=1/2!

For you battery geeks, you can verify these numbers by calculating the theoretical energy of the battery using the 98 mAh/g and multiplying by 3.7 V to get 360 Wh/kg (the theoretical capacity of a graphite/LiCoO2 cell). You can calculate the practical capacity by multiple 49 mAh/g by 3.7 V to get ~180 Wh/kg (A typical value for a 18650 cell using cobalt oxide). Well well well... the math works, does it not?

Here is the rub. Remember the example where we had an anode that has 10x the capacity. We had a cell capacity of 134 mAh/g. If you do the calculation for the extra weight and recalculate the capacity you get only 55 mAh/g.

You have to think about this a little bit, but it turns out that if you have more capacity you will need less of the anode, so now the inactive weight becomes a larger fraction of the total weight of the battery. You could have compensated for this by taking the same weight of the anode and just talking a lot more cathode, but like I was saying, this is impossible because it increases the losses in the battery to a point where it would be useless.

So we have an anode with 10x the capacity and we gain 12% in cell capacity (and don't get me started on the voltage! That is for another post).

If you don't believe me, do the math. If you don't know how to do the math; I guess you have to believe me! It would be embarrassing if someone spots an error; but then again I'm assuming that no one has actually made it this far.

If you do the same math on the battery where instead of the anode being better, the cathode is twice the capacity, where we calculated a cell capacity of 151 mAh/g without the inactive weight you will calculate a cell capacity of 68 mAh/g with the inactive material. So you made a cathode of twice the capacity and your cell capacity actually went up by 38% (remember we calculated this to be 50% better before).

Turns out that even if you make a battery with 3300 mAh/g for the anode (in a sense, this is close to the best Li-ion anode we know of) and a cathode of 280 mAh/g (the best Li-ion cathode we know of) we get a cell capacity of 110 mAh/g. 2.2x the present-day battery. But this assumes the voltage of the two are the same. In reality the materials that have this capacity have a lower voltage, which means that the energy is not really that high. Turns out that this best base scenario battery is better by maybe a factor of 1.8 to 1.9. Meaning, this battery will approach 340 Wh/kg.

*Geek meter off*

As a matter of fact, everything else being equal (i.e., amount of inactive material), the best Li-ion battery we can dream of making in the future, based on what we know as of late June 2010, will have a energy density of ~340 Wh/kg. If you want something better, you pretty much have to work on the inactive material. All these are for cell-level numbers. If you go to a battery pack, things get even worse, but that is for another post. If someone tells you that they can make a battery where the energy is greater than this, you better dig.

Most people, including battery researchers, don't think about this extra weight. Its actually a very important factor in a battery. There is such a great focus on new materials that folks forget that reality may be as good as your simple math leads you to believe. In addition to new materials, we have to think about ways to decrease the inactive materials in a battery. There is far too little research on this and a lot to be gained from doing something about it.

So next time you hear about a new material with more capacity, ask not how much more theoretical capacity you can get, instead ask how much practical energy you actually get. Remember that you can't just divide theory by 2 to get practical; it could be less (a lot less). And don't forget the voltage. Its also critical.

To help you, here is a link to a excel spreadsheet that has a battery simulator specifically for a lithium-ion battery. I hope the mac version of excel is compatible with a PC. The sheet that has the calculations is protected. Contact me to unprotect. Let me know if you catch errors. The simulator makes a LOT of assumptions. If you want them all relaxed, contact me.

Venkat